Dyes containing thiophene radicals

ABSTRACT

The compounds of the general formula I ##STR1## where X is fluorine, chlorine, bromine, SO 2  E or unsubstituted or substituted hydroxyl or mercapto, E is alkyl, alkenyl, cycloalkyl, aralkyl, aryl, chlorine or unsubstituted or substituted hydroxyl or amino, Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl, T is hydrogen, C 1  -C 4  -alkyl, a radical which can be introduced by electrophilic substitution or a radical of the formula --CH═B, in which B is a radical of a methylene-active compound or of an amine, and K is a radical of a coupling component, are very useful for dyeing synthetic fibers or plastics.

This is a continuation of application Ser. No. 07/884,472, filed May 13, 1992, now U.S. Pat. No. 5,283,326 which is a continuation of application Ser. No. 07/532,663, filed Jun. 4, 1990, now abandoned which is division of application Ser. No. 07/205,359, filed Jul. 27, 1988, now abandoned, which is a division of application Ser. No. 06/860,573, filed May 7, 1986, now abandoned.

The present invention relates to compounds of the general formula I ##STR2## where X is fluorine, chlorine, bromine, SO₂ E or unsubstituted or substituted hydroxyl or mercapto, E is alkyl, alkenyl, cycloalkyl, aralkyl, aryl, chlorine or unsubstituted or substituted hydroxyl or amino, Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl, T is hydrogen, C₁ -C₄ -alkyl, a radical which can be introduced by electrophilic substitution or a radical of the formula --CH═B, in which B is a radical of a methylene-active compound or of an amine, and K is a radical of a coupling component.

Examples of radicals X, in addition to those stated above, are alkoxy, cycloalkoxy, aralkoxy and aryloxy, as well as the corresponding mercapto radicals. Specific examples are OH, OCH₃, OC₂ H₅, OC₃ H₇, OC₄ H₉, OCH₂ C₆ H₅, OC₆ H₁₁, OC₆ H₅, OC₆ H₄ CH₃, OC₆ H₄ Cl, SH, SCH₃, SC₂ H₅, SC₃ H₇, S₄ H₉, SCH₂ C₆ H₅, SC₂ H₄ OH, SCH₂ COOCH₃, SH₂ COOC₂ H₅, SC₆ H₁₁, SC₆ H₅ and SC₆ H₄ CH₃.

E is, for example, CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₆ H₁₃, C₆ H₁₁, C₈ H₁₇, C₆ H₅ --CH₂, C₆ H₅ --CH₂ --CH₂, C₆ H₅, Cl--C₆ H₄, C₄ H₉ --C₆ H₄, Cl, OH, CH₃ O, C₂ H₅ O, C₃ H₇ O, C₄ H₉ O, C₆ H₅ --CH₂ O, C₆ H₅ --CH₂ --CH₂ O, C₆ H₅ O, ClC₆ H₄ O, CH₃ C₆ H₄ O, NH₂, NHCH₃, N(CH₃)₂, NHC₂ H₅, N(C₂ H₅)₂, NHC₄ H₉, N(C₄ H₉)₂, NHC₆ H₅, NHC₆ H₄ --CH₃, NHC₆ H₄ Cl or NCH₃ C₆ H₄.

Specific examples of radicals Y, in addition to those stated above, are: ##STR3##

Examples of radicals T which can be introduced by electrophilic substitution are Cl, Br, NO, NO₂, SO₃ H, CHO, CN and acyl, where acyl is, for example CH₃ CO, C₂ H₅ CO, C₆ H₅ CO, CH₃ SO₂, C₂ H₅ SO₂ or C₆ H₅ SO₂.

Methylene-active compounds of the formula H₂ B are, for example, compounds of the formula ##STR4## where Z is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl or is a radical of a compound of the formula ##STR5##

Specific examples of important compounds of the formula ##STR6##

Examples of amine radicals B are ═N--C₆ H₅, ═N--C₆ H₄ CH₃ or generally radicals of Schiff's bases of the amines.

Alkyl radicals T are, for example, CH₃, C₂ H₅, C₃ H₇ or C₄ H₉.

The diazo components in which T is H or C₁ -C₄ -alkyl alkyl can be prepared by reacting a compound of the formula II ##STR7## with a sulfur donor. Radicals T may be introduced into the diazo components in which T is H by electrophilic substitution by a conventional method.

Furthermore, the diazo component in which T is H and X is OH may be prepared by reacting the compound of the formula

    CLCH.sub.2 COCL

with malodinitrile and then reacting the product with a sulfide.

The preparation of the diazo components is described in detail in European Patent Application 86102603.7.

The coupling components of the formula HK are preferably derived from the aniline, α-naphthylamine, pyrazole, aminopyrazole, indole, thiazole, thiophene, phenol, naphthol, tetrahydroquinoline, pyridone or pyridine series, those of the aniline, pyrazole, pyridine, thiophene and thiazole series being preferred.

The coupling components HK are in particular of the general formula ##STR8## where B¹ is hydrogen or B², B² is unsubstituted or substituted alkyl, cycloalkyl, alkenyl, aryl or acyl, R¹ is hydrogen, alkyl, aralkyl or aryl, R² is hydrogen or R³, R³ is unsubstituted or substituted alkyl, cycloalkyl, alkenyl, aralkyl or aryl, R⁴ and R⁵ independently of one another are each hydrogen, alkyl, alkoxy, phenoxy, halogen, alkylsulfonylamino, dialkylaminosulfonylamino or acylamino, R⁶ is cyano, carbamyl, nitro, acetyl or carbalkoxy and R⁷ is unsubstituted or substituted phenyl, alkyl, aralkyl, halogen, substituted hydroxyl or mercapto.

Examples of radicals B², in addition to those stated above, are C₁ -C₆ -alkyl which may be substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, phenyl, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenylethoxycarbonyl, and phenyl and cyclohexyl.

Specific examples of radicals B² are:

1) Unsubstituted or substituted alkyl, such as ##STR9## and the corresponding radicals in which two C₂ H₄ O, C₃ H₆ O, ##STR10## groups are present, and ##STR11##

2. Unsubstituted or substituted cycloalkyl: ##STR12##

3. Unsubstituted or substituted aralkyl: ##STR13## and those radicals containing C₆ H₄ CH₃ and C₆ H₄ OCH₃ instead of C₆ H₅.

4. Unsubstituted or substituted phenyl: C₆ H₅, C₆ H₄ CH₃, C₆ H₃ (CH₃)₂, C₆ H₄ OCH₃, C₆ H₃ (OCH₃)₂, C₆ H₄ Cl and C₆ H₂ (OCH₃)₂ Cl.

5. The radicals CH₂ CH=CH₂, CH₂ COOCH₃, (CH₂)₅ COOCH₃, (CH₂)₅ COOC₂ H₅, ##STR14## where n is 2, 3, 4 or 6.

6. Acyloxy radicals: (CH₂)₂ OCHO, (CH₂)₂ OCO(CH₂)_(n) CH₃, (C₂ H₄ O)₂ CHO, (C₂ H₄ O)₂ CO(CH₂)_(n) CH₃, (CH₂)₃ O(CH₂)₂ OCHO, (CH₂)₃ O(CH₂)₂ OCO(CH₂)_(n) CH₃, (CH₂)₂ O(CH₂)₄ OCHO and (CH₂)₂ O(CH₂)₄ OCO(CH₂)_(n) CH₃, where n is 0 to 7, ##STR15## and the corresponding radicals containing (CH₂)₃ or (CH₂)₄ instead of (CH₂)₂.

7. Acyl radicals: CHO and CH₃ (CH₂)_(n) CO, where n is from 0 to 7, C₆ H₅ CO, CH₃ C₆ H₄ CO, C₆ H₅ CH₂ CO, C₆ H₅ OCH₂ CO, CH₃ SO₂, C₂ H₅ SO₂, C₆ H₅ SO₂ and CH₃ C₆ H₄ SO₂.

Specific examples of radicals R¹, in addition to those stated above, are methyl, ethyl, propyl, butyl, benzyl, phenethyl, phenyl, o-, m- and p-tolyl and o-, m- and p-chlorophenyl.

Examples of radicals R³, in addition to those mentioned above, are C₁ -C₆ -alkyl which may be substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- and p-methylbenzoyloxy, o-, m- and p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenylethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenylethoxycarbonyl, and phenyl, benzyl, phenethyl and cyclohexyl.

Specific examples of radicals R³ are methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, methallyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonlyoxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-β-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl and 2-benzoylethyl.

Examples of suitable radicals R⁴ and R⁵ are hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy and C₁ -C₄ -alkoxycarbonylamino, and benzoylamino or C₁ -C₆ -alkanoylamino which is unsubstituted or substituted by chlorine, bromine, cyano, methoxy, ethoxy or phenoxy, and C₁ -C₄ -alkylsulfonylamino or -dialkylaminosulfonylamino.

Examples of radicals R⁶ in addition to those mentioned above are aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n- and isopropoxycarbonyl, n-, iso- and sec.-butoxycarbonyl, methoxyethoxycarbonyl ethoxyethoxycarbonyl, n- and isopropoxyethoxycarbonyl and n-, iso- and sec.-butoxyethoxycarbonyl.

Examples of radicals R⁷ are C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, phenoxy, benzyloxy, phenyl, chlorine, bromine, nitro, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -mono-and dialkylamino, C₁ -C₄ -alkoxyethoxy, C₁ -C₄ -alkyl- or phenylmercapto, C₁ -C₅ -alkanoylamino, such as acetylamino, propionylamino, butyrylamino or valerylamino, monosubstituted or polysubstituted phenyl, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonylmethyl, cyanomethyl and benzyl.

The compounds of the formula I have yellow to greenish blue hues and are particularly useful for dyeing polyesters, nylons, cellulose esters and blends of polyesters and cellulose fibers. As a rule, the dyeings obtained have good or very good fastness properties, particularly on polyesters.

Dyes having a suitable constitution are dischargeable under reduced conditions and/or under alkaline and reducing conditions.

Suitable discharging agents are the conventionally used ones, for example tin(II) chloride, sodium bisulfite, sodium dithionite or hydroxymethanesulfonic acid. The discharge process too can be carried out in a conventional manner.

Some of the compounds of the formula I are very useful for dyeing thermoplastics, such as polystyrene, polymethacrylates, polycarbonates, nylon and styrene/acrylic acid/butadiene copolymers, since they possess high color strength and good lightfastness and heat resistance. Furthermore, many novel dyes can be used for dyeing and/or printing polyester/cotton blends by the process described in German Patent 1,811,796, the resulting dyeings having good lightfastness and fastness to washing.

The compounds of the formula I can be prepared by a conventional method. Details are given in the Examples, in which parts and percentages are by weight, unless started otherwise.

Of particular importance are compounds of the formulae I a ##STR16## and I b ##STR17## where X¹ is chlorine, bromine, hydroxyl, C₁ -C₄ -alkoxy or -alkylthio, methylsulfonyl, phenylsulfonyl, phenoxy or phenylthio, Y¹ and Z¹ are each cyano, a carboxylic ester group or substituted carbamyl, T¹ is formyl, nitro or cyano and K¹ is a radical of a coupling component of the aniline, thiazole, pyrazole, thiophene or pyridine series.

Compounds of the formulae Ia and Ib in which X¹ is chlorine, ethoxy or phenylmercapto, Y¹ is cyano, T¹ is formyl, Z¹ is cyano, a carboxylic ester group or substituted carbamyl and K is a radical of a coupling component of the aniline, thiazole, thiophene or pyridine series, are particularly useful industrially.

Other particularly important dyes are those of the general formula IIa ##STR18## where X¹, Y¹ and T¹ have the stated meanings, B³ is hydrogen or B⁴, and B⁴ is C₂ -C₈ -alkyl which may or may not be interrupted by oxygen and is unsubstituted or substituted by hydroxyl, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxy, benzyloxy or phenoxy, or is phenyl which is unsubstituted or substituted by methyl or methoxy. Preferred carboxylic ester groups Y¹ are COOCH₃ and COOC₂ H₅.

Examples of particularly preferred radicals B³ and B⁴ are hydrogen and C₂ H₅, C₃ H₇, C₄ H₉, ##STR19## C₆ H₁₁, C₆ H₅, C₆ H₄ CH₃, C₆ H₄ OCH₃, C₂ H₄ OH, C₃ H₆ OH, C₂ H₄ OCH₃, C₃ H₆ OCH₃, C₂ H₄ OC₂ H₅, C₂ H₄ OC₄ H₉, C₃ H₆ OC₂ H₅, C₂ H₄ OC₂ H₄ OH, C₃ H₆ OC₂ H₄ OH, C₃ H₆ OC₄ H₈ OH, C₃ H₈ OC₂ H₄ OCH₃, C₃ H₆ OC₂ H₅, C₃ H₆ OC₂ H₄ OC₄ H₉, C₃ H₆ OC₄ H₈ OC₂ H₅, C₃ H₆ OC₄ H₈ OC₄ H₉, C₂ H₄ OC₂ H₄ OCO(CH₂)_(m) CH₃, C₃ H₆ OC₂ H₄ OCO(CH₂)_(m) CH₃, C₃ H₆ OC₄ H.sub. 8 OCO(CH₂)_(m) CH₃, C₂ H₄ OCO(CH₂)_(m) CH₃. C₃ H₆ OCO(CH₂)_(m) CH₃, C₃ H₆ OCH₂ C₆ H₅ and C₃ H₆ OC₂ H₄ OC₆ H₅, where m is from 1 to 4.

Examples of particularly preferred combinations of B³ and B⁴ are hydrogen and C₂ H₄ OC₂ H₄ OCOCH₃, C₂ H₄ OC₂ H₄ OCOC₂ H₅, C₃ H₆ OC₄ H₈ OH, ,C₃ H₆ OC₄ H₈ OCOCH₃,.C₃ H₆ OC₄ H₈ OCOC₂ H₅, C₃ H₆ OC₂ H₄ OCH₃, C₃ H₆ OC₂ H₄ OC₂ H₅, C₃ H₆ OC₂ H₄ OC₄ H₉, C₃ H₆ OC₄ H₈ OC₂ H₅, C₃ H₆ OC₄ H₈ OC₄ H₉, C₃ H₆ OCH₂ C₆ H₅, C₃ H₆ OC₂ H₄ OC₆ H₅ or C₃ H₆ OCH₂ -CH(C₂ H₅)C₄ H₉, and C₂ H₅, C₂ H₄ OCH₃, C₃ H₆ OCH₃, CH(CH₃)₂ or C₄ H₉ in combination with C₂ H₄ OC₂ H₄ OCOCH₃, C₃ H₆ OC₄ H₈ OH, C₃ H₆ OC₄ H₈ OCHO, C₃ H₆ OC₄ H₈ OCOCH₃, C₃ H₆ OC₄ H₈ OCOC₂ H₅, C₃ H₆ OC₂ H₄ OC₄ H₉, C₃ H₆ OC₄ H₈ OC₂ H₅, C₃ H₆ OC₄ H₈ OC₄ H₉ or C₃ H₆ OC₂ H₄ OC₆ H₅ and furthermore C₂ H₄ OH, C₃ H₆ OH, C₂ H₄ OCOCH₃, C₂ H₄ OCOC₂ H₅, C₃ H₆ OCOCH₃ or C₃ H₆ OCOC₂ H₅ in combination with C₃ H₆ OC₂ H₄ OCH₃, C₃ H₆ OC₂ H₄ OC₂ H₅, C₃ H₆ OC₂ H₄ OC₄ H₉ , C₃ H₆ OC₄ H₈ OC₂ H₅, C₃ H₆ OC₄ H₈ OC₄ H₉, C₆ H₄ OCH₃ or C₆ H₅.

The process for the preparation of acyloxyalkyl-substituted or acyloxyalkoxyalkyl-substituted 2,6-diaminopyridines which are free of by-products is also particularly important.

Previously, azo dyes containing such coupling components had to be prepared by subsequent acylation of the corresponding hydroxyl-containing dyes in anhydrous organic solvents with acyl halides or anhydrides since the coupling components themselves preferentially undergo N-acylation under these conditions, and the N-acyl-2,6-diaminopyridines are not capable of coupling.

According to the invention, the coupling components are prepared by adding not less than an equivalent amount of sulfuric acid to a solution or suspension of the hydroxyl-containing substituted pyridine in the desired organic acid and stirring the mixture at from 20° to 100° C., preferably from 20° to 50° C. The degree of acylation is dependent on the water content and reaches 100% in an anhydrous medium. However, the absence of water and 100% conversion are not essential in every case in order to achieve optimum dyeing properties. An adequate conversion in most cases is 70-70%, which does not require the absence of water and advantageously allows the acylation to be combined with the preparation of the hydroxyalkylaminopyridine.

EXAMPLE 1

4.7 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene in 30 parts by volume of 85% strength sulfuric acid were stirred at no higher than 30° C., 8.3 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were added dropwise at 0°-5° C., and the mixture was then stirred for a further 4 hours at this temperature.

The resulting diazonium salt solution was slowly run, at 0° C., into a solution of 5.8 parts of N,N-diallyl-3-aminoacetanilide in a mixture of 25 parts by volume of dimethylformamide, 125 parts of water, 300 parts of ice, 20 parts by volume of 32% strength hydrochloric acid and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried to give 9 parts of the dye of the formula ##STR20## which dyes polyester fibers in fast blue hues.

EXAMPLE 2

4.7 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene were diazotized by a method similar to that described in Example 1. The diazonium salt solution was added dropwise at 0° C., to a solution of 8.8 parts of o-(bisacetoxyethyl)-amino-p-acetanisidine in a mixture of 125 parts of water, 350 of ice, 1 part of 96% strength sulfuric acid and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered under suction, washed until neutral and dried to give 9.5 parts of a greenish black powder of the formula ##STR21## which dyes polyester fabric in fast greenish blue hues.

The dyes characterized in the Table below are obtained similarly to Examples 1 and 2.

    __________________________________________________________________________      ##STR22##                                                                     Example                                  Dyeing on                             No.  T    X Y      K                     polyester                             __________________________________________________________________________      3   CHO  Cl                                                                               CN                                                                                     ##STR23##            blue                                   4   CHO  Cl                                                                               CN                                                                                     ##STR24##            bluish violet                          5   CHO  Cl                                                                               CN                                                                                     ##STR25##            blue                                   6   CHO  Cl                                                                               CN                                                                                     ##STR26##            blue                                   7   CHO  Cl                                                                               CN                                                                                     ##STR27##            blue                                   8   CHO  Cl                                                                               CN                                                                                     ##STR28##            blue                                   9   CHO  Cl                                                                               CN                                                                                     ##STR29##            blue                                  10   CHO  Cl                                                                               CN                                                                                     ##STR30##            blue                                  11   CHO  Cl                                                                               CN                                                                                     ##STR31##            reddish blue                          12   CHO  Cl                                                                               CN                                                                                     ##STR32##            reddish blue                          13   CHO  Cl                                                                               CN                                                                                     ##STR33##            bluish violet                         14   CHO  Cl                                                                               CN                                                                                     ##STR34##            violet                                15   CHO  Cl                                                                               CN                                                                                     ##STR35##            greenish blue                         16   CHO  Cl                                                                               CN                                                                                     ##STR36##            greenish blue                         17   CHO  Cl                                                                               CN                                                                                     ##STR37##            greenish blue                         18   CHO  Cl                                                                               CN                                                                                     ##STR38##            greenish blue                         19   CHO  Cl                                                                               CN                                                                                     ##STR39##            greenish blue                         20   CHO  Cl                                                                               CN                                                                                     ##STR40##            greenish blue                         21   CHO  Cl                                                                               CN                                                                                     ##STR41##            greenish blue                         22   CHO  Cl                                                                               CN                                                                                     ##STR42##            blue                                  23   CHO  Cl                                                                               CN                                                                                     ##STR43##            blue                                  24   CHO  Cl                                                                               CO.sub.2 C.sub.2 H.sub.5                                                               ##STR44##            blue                                  25   CHO  Cl                                                                               CN                                                                                     ##STR45##            blue                                  26   CHO  Cl                                                                               CN                                                                                     ##STR46##            blue                                  27   CHO  Cl                                                                               CN                                                                                     ##STR47##            blue                                  28   CHO  Cl                                                                               CN                                                                                     ##STR48##            blue                                  29   CHO  Cl                                                                               CN                                                                                     ##STR49##            blue                                  30   CHO  Cl                                                                               CN                                                                                     ##STR50##            blue                                  31   CHO  Cl                                                                               COOCH.sub.3                                                                            ##STR51##            blue                                  32   CHO  Cl                                                                               SO.sub.2 CH.sub.3                                                                      ##STR52##            blue                                  33   CHO  Cl                                                                               CONH.sub.2                                                                             ##STR53##            reddish blue                          34   CHO  Cl                                                                               CON(CH.sub.3).sub.2                                                                    ##STR54##            blue                                  35   CHO  Cl                                                                               CO.sub.2 C.sub.2 H.sub.5                                                               ##STR55##            blue                                  36   CHO  Cl                                                                               CO.sub.2 C.sub.2 H.sub.5                                                               ##STR56##            bluish violet                         37   CHO  Cl                                                                               CO.sub.2 C.sub.2 H.sub.5                                                               ##STR57##            blue                                  38   CHO  Cl                                                                               CO.sub.2 C.sub.2 H.sub.5                                                               ##STR58##            greenish blue                         39   CHO  Br                                                                               CN                                                                                     ##STR59##            violet                                40   CHO  Br                                                                               CN                                                                                     ##STR60##            bluish violet                         41   CHO  Br                                                                               CN                                                                                     ##STR61##            blue                                  42   CHO  Br                                                                               CN                                                                                     ##STR62##            greenish blue                         43   CHO  Br                                                                               CO.sub.2 C.sub.2 H.sub.5                                                               ##STR63##            blue                                  44   CHO  F CN                                                                                     ##STR64##            blue                                  45   CHO  F CN                                                                                     ##STR65##            reddish blue                          46   CHO  F CN                                                                                     ##STR66##            blue                                  47   CHO  F CO.sub.2 C.sub.2 H.sub.5                                                               ##STR67##            reddish blue                          48   CHO  Cl                                                                               CO.sub.2 C.sub.2 H.sub.5                                                               ##STR68##            blue                                  49   CHO  Cl                                                                               CONH.sub.2                                                                             ##STR69##            blue                                  50   CHO  Cl                                                                               NO.sub.2                                                                               ##STR70##            blue                                  51   CHO  Cl                                                                               CON(CH.sub.3).sub.2                                                                    ##STR71##            blue                                  52   CHO  Cl                                                                               SO.sub.2 CH.sub.3                                                                      ##STR72##            blue                                  53   CHO  Br                                                                               CO.sub.2 C.sub.2 H.sub.5                                                               ##STR73##            blue                                  54   CHO  Cl                                                                               CN                                                                                     ##STR74##            blue                                  55   CHO  Cl                                                                               CN                                                                                     ##STR75##            blue                                  56   CHO  Br                                                                               CN                                                                                     ##STR76##            blue                                  57   CHO  Cl                                                                               CN                                                                                     ##STR77##            violet                                58   CHO  Cl                                                                               CN                                                                                     ##STR78##            blue                                  59   CHO  Cl                                                                               CO.sub.2 C.sub.2 H.sub.5                                                               ##STR79##            blue                                  60   CHO  Cl                                                                               CN                                                                                     ##STR80##            yellowish brown                       61   CHO  Cl                                                                               CN                                                                                     ##STR81##            red                                   62   CHO  Cl                                                                               CN                                                                                     ##STR82##            red                                   63   CHO  Cl                                                                               CN                                                                                     ##STR83##            blue                                  64   CHO  Cl                                                                               CN                                                                                     ##STR84##            blue                                  65   CHO  Br                                                                               CN                                                                                     ##STR85##            blue                                  66   CHO  Cl                                                                               CN                                                                                     ##STR86##            blue                                  67   CHO  Cl                                                                               CN                                                                                     ##STR87##            violet                                68   CHO  Cl                                                                               CN                                                                                     ##STR88##            red                                   69   CHO  Cl                                                                               CN                                                                                     ##STR89##            red                                   70   CHO  Cl                                                                               CN                                                                                     ##STR90##            blue                                  71   CHO  Cl                                                                               CN                                                                                     ##STR91##            blue                                  72   H    Cl                                                                               CN                                                                                     ##STR92##            red                                   73   CH.sub.3                                                                            Cl                                                                               CN                                                                                     ##STR93##            red                                   74   CH.sub.3                                                                            Cl                                                                               CN                                                                                     ##STR94##            red                                   75   CH.sub.3                                                                            Cl                                                                               CN                                                                                     ##STR95##            reddish violet                        76   C.sub.2 H.sub.5                                                                     Cl                                                                               CN                                                                                     ##STR96##            red                                   77   CH.sub.3                                                                            Br                                                                               CN                                                                                     ##STR97##            red                                   78   CN   Cl                                                                               CN                                                                                     ##STR98##            blue                                  79   CN   Cl                                                                               CN                                                                                     ##STR99##            blue                                  80   CN   Cl                                                                               CN                                                                                     ##STR100##           greenish blue                         81   CN   Br                                                                               CN                                                                                     ##STR101##           reddish blue                          82   CN   Cl                                                                               CN                                                                                     ##STR102##           blue                                  83   NO.sub.2                                                                            Cl                                                                               CN                                                                                     ##STR103##           reddish blue                          84   NO.sub.2                                                                            Cl                                                                               CN                                                                                     ##STR104##           blue                                  85   NO.sub.2                                                                            Cl                                                                               CN                                                                                     ##STR105##           greenish blue                         86   NO.sub.2                                                                            Cl                                                                               CN                                                                                     ##STR106##           greenish blue                         87                                                                                   ##STR107##                                                                         Cl                                                                               CN                                                                                     ##STR108##           blue                                  88   NO.sub.2                                                                            Br                                                                               CN                                                                                     ##STR109##           blue                                  89   NO.sub.2                                                                            Cl                                                                               CN                                                                                     ##STR110##           greenish blue                         90   NO.sub.2                                                                            Cl                                                                               CN                                                                                     ##STR111##           greenish blue                         91   Br   Cl                                                                               CN                                                                                     ##STR112##           bluish red                            92   Br   Cl                                                                               CN                                                                                     ##STR113##           bluish violet                         93   Br   Cl                                                                               CN                                                                                     ##STR114##           red                                   94   Br   Cl                                                                               CN                                                                                     ##STR115##           red                                   95   Br   Cl                                                                               CN                                                                                     ##STR116##           bluish violet                         96   Cl   Cl                                                                               CN                                                                                     ##STR117##           bluish red                            97   Cl   Cl                                                                               CN                                                                                     ##STR118##           reddish blue                          98   Br   Br                                                                               CN                                                                                     ##STR119##           reddish blue                          __________________________________________________________________________

EXAMPLE 99

11.7 parts of 2-amino-3-cyano-4-ethoxy-5-formylthiophene in 200 parts by volume of a 3:1 glacial acetic acid/propionic acid mixture and 25 parts by volume of 96% strength sulfuric acid were stirred at no higher than 20° C. 23 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were added dropwise at 0°-5° C., and the mixture was then stirred for 1 hour.

The resulting diazonium salt solution was added dropwise, at 0° C., to a solution of 21 parts of o-(bisacetoxyethyl)-amino-p-acetanisidine in a mixture of 100 parts by volume of dimethylformamide, 500 parts of water, 25 parts by volume of 18% strength hydrochloric acid, 250 parts of ice and 1 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried to give 25 parts of the dye of the formula ##STR120## which dyes polyester fibers in fast greenish blue hues.

The dyes shown in the Table below were obtained similarly to Example 99.

    __________________________________________________________________________      ##STR121##                                                                    Example No.                                                                           T   X   Y      K                     Dyeing on polyester                __________________________________________________________________________     100    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR122##           blue                               101    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR123##           bluish violet                      102    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR124##           blue                               103    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR125##           blue                               104    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR126##           blue                               105    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR127##           blue                               106    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR128##           reddish blue                       107    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR129##           reddish blue                       108    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR130##           bluish violet                      109    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR131##           violet                             110    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR132##           greenish blue                      111    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR133##           greenish blue                      112    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR134##           greenish blue                      113    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR135##           greenish blue                      114    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR136##           blue                               115    CHO OC.sub.2 H.sub.5                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR137##           blue                               116    CHO OC.sub.2 H.sub.5                                                                   COOCH.sub.3                                                                            ##STR138##           blue                               117    CHO OC.sub.2 H.sub.5                                                                   SO.sub.2 CH.sub.3                                                                      ##STR139##           blue                               118    CHO OC.sub.2 H.sub.5                                                                   CONH.sub.2                                                                             ##STR140##           reddish blue                       119    CHO OC.sub.2 H.sub.5                                                                   CON(CH.sub.3).sub.2                                                                    ##STR141##           blue                               120    CHO OC.sub.2 H.sub.5                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR142##           blue                               121    CHO OC.sub.2 H.sub.5                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR143##           bluish violet                      122    CHO OC.sub.2 H.sub.5                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR144##           blue                               123    CHO OC.sub.2 H.sub.5                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR145##           greenish blue                      124    CHO OCH.sub.3                                                                          CN                                                                                     ##STR146##           violet                             125    CHO OCH.sub.3                                                                          CN                                                                                     ##STR147##           bluish violet                      126    CHO OCH.sub.3                                                                          CN                                                                                     ##STR148##           blue                               127    CHO OCH.sub.3                                                                          CN                                                                                     ##STR149##           greenish blue                      128    CHO OCH.sub.3                                                                          CO.sub.2 C.sub.2 H.sub.5                                                               ##STR150##           blue                               129    CHO OC.sub.6 H.sub.5                                                                   CN                                                                                     ##STR151##           blue                               130    CHO OC.sub.6 H.sub.5                                                                   CN                                                                                     ##STR152##           bluish violet                      131    CHO SC.sub.6 H.sub.5                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR153##           blue                               132    CHO SC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR154##           bluish violet                      133    CHO SC.sub.6 H.sub.5                                                                   CN                                                                                     ##STR155##           blue                               134    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR156##           blue                               135    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR157##           blue                               136    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR158##           blue                               137    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR159##           reddish blue                       138    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR160##           blue                               139    CHO OCH.sub.3                                                                          CO.sub.2 C.sub.2 H.sub.5                                                               ##STR161##           blue                               140    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR162##           yellowish brown                    141    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR163##           red                                142    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR164##           red                                143    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR165##           blue                               144    CHO OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR166##           blue                               145    CHO OCH.sub.3                                                                          CN                                                                                     ##STR167##           blue                               146    CHO OC.sub.6 H.sub.5                                                                   CN                                                                                     ##STR168##           blue                               147    CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR169##           red                                148    CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR170##           red                                149    CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR171##           reddish violet                     150    C.sub.2 H.sub.5                                                                    OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR172##           red                                151    CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR173##           red                                152    CN  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR174##           blue                               153    CN  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR175##           blue                               154    NO.sub.2                                                                           OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR176##           blue                               __________________________________________________________________________

EXAMPLE 155

5.8 parts of the dye described in Example 12 were dissolved in 60 parts by volume of dioxane, 3.4 parts of ethyl cyanoacetate, 1 part of glacial acetic acid and 1 part of piperidine were added, and the mixture was stirred for 16 hours at room temperature, after which 50 parts of water and 50 parts of ice were added. Stirring was continued for 15 minutes, and the product was filtered off under suction, washed neutral and dried at 50° C. under reduced pressure to give 6.6 parts of the dye of the formula ##STR177## which dyes polyester fibers in medium blue hues.

EXAMPLE 156

5.1 parts of the dye described in Example 13 were dissolved in 65 parts by volume of dioxane, 4.2 parts of butyl cyanoacetate, 1 part of glacial acetic acid and 1 part of piperidine were added and the mixture was stirred for 16 hours at room temperature. Thereafter, 50 parts of water and 50 parts of ice were added, stirring was continued for 1 hour and the product was filtered off under suction, washed neutral and dried to give 5.9 parts of the dye of the formula ##STR178## which dyes polyester in fast blue hues.

The dyes listed in the Table below were obtained similarly to Examples 155 and 156.

    __________________________________________________________________________      ##STR179##                                                                    Example                                                  Dyeing on             No.  X   Y      Y.sup.1                                                                              Y.sup.2     K                      polyester             __________________________________________________________________________     157  Cl  CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                          ##STR180##            blue                  158  Cl  CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                          ##STR181##            reddish blue          159  Cl  CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                          ##STR182##            blue                  160  Cl  CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                          ##STR183##            blue                  161  Cl  CN     CN    CN                                                                                          ##STR184##            blue                  162  Cl  CN     COCH.sub.3                                                                           COOC.sub.2 H.sub.5                                                                          ##STR185##            blue                  163  Cl  COOC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                          ##STR186##            blue                  164  Cl  COOC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                          ##STR187##            blue                  165  Cl  COOC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                          ##STR188##            blue                  166  Cl  COOC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                          ##STR189##            dark blue             167  Cl  COOC.sub.2 H.sub.5                                                                    COCH.sub.3                                                                           COOC.sub.2 H.sub.5                                                                          ##STR190##            dark blue             168  Cl  COOC.sub.2 H.sub.5                                                                    COCH.sub.3                                                                           COCH.sub.3                                                                                  ##STR191##            blue                  169  Cl  COOC.sub.2 H.sub.5                                                                    COCH.sub.3                                                                           CN                                                                                          ##STR192##            dark blue             170  Cl                                                                                  ##STR193##                                                                           CN    COOC.sub.2 H.sub.5                                                                          ##STR194##            dark blue             171  Cl                                                                                  ##STR195##                                                                           CN    COOC.sub.2 H.sub.5                                                                          ##STR196##            blue                  172  Cl  SO.sub.2 CH.sub.3                                                                     CN    COOC.sub.2 H.sub.5                                                                          ##STR197##            dark blue             173  Cl  SO.sub.2 CH.sub.3                                                                     CN    COOC.sub.2 H.sub.5                                                                          ##STR198##            blue                  174  Cl  SO.sub.2 CH.sub.3                                                                     CN    COOC.sub.2 H.sub.5                                                                          ##STR199##            blue                  175  Cl  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR200##            reddish blue          176  Cl  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR201##            dark blue             177  Cl  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR202##            dark blue             178  Cl  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR203##            dark blue             179  Cl  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR204##            dark blue             180  Cl  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR205##            dark blue             181  Cl  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR206##            blue                  182  Cl  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR207##            blue                  183  Cl  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR208##            blue                  184  Cl  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR209##            blue                  185  Cl  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR210##            violet                186  Cl  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR211##            violet                187  Cl  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR212##            violet                188  Cl  CN     CN    CONHCH.sub.3                                                                                ##STR213##            dark blue             189  Cl  CN     CN    CONHC.sub.2 H.sub.5                                                                         ##STR214##            dark blue             190  Cl  CN     CN    SO.sub.2 CH.sub.3                                                                           ##STR215##            dark blue             191  Cl  CN     CN    COCH.sub.3                                                                                  ##STR216##            dark blue             192  Cl  CN     CN    COOCH.sub.3                                                                                 ##STR217##            dark blue             193  Cl  CN     CN    COOC.sub.4 H.sub.9 (n)                                                                      ##STR218##            blue                  194  Cl  CN     CN    COOC.sub.4 H9(n)                                                                            ##STR219##            blue                  195  Cl  CN     CN    COOC.sub.4 H.sub.9 (n)                                                                      ##STR220##            blue                  196  Cl  CN     CN    COOC.sub.4 H.sub.9 (n)                                                                      ##STR221##            dark blue             197  Cl  CN     CN                                                                                    ##STR222##                                                                                 ##STR223##            dark blue             198  Cl  CN     CN                                                                                    ##STR224##                                                                                 ##STR225##            dark blue             199  Cl  CN     CN                                                                                    ##STR226##                                                                                 ##STR227##            dark blue             200  Cl  CN     CN    CONH.sub.2                                                                                  ##STR228##            dark blue             201  Cl  CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                          ##STR229##            navy blue             202  Cl  CN     COCH.sub.3                                                                           COOC.sub.2 H.sub.5                                                                          ##STR230##            dark blue             203  Cl  CN     CN    CONHCH.sub.3                                                                                ##STR231##            dark blue             204  Br  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR232##            reddish blue          205  Br  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR233##            reddish blue          206  Br  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR234##            blue                  207  Br  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR235##            dark blue             208  Br  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR236##            dark blue             209  Br  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR237##            dark blue             210  Br  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR238##            dark blue             211  Br  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR239##            dark blue             212  Br  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR240##            dark blue             213  Br  CN     CN    COOC.sub.4 H.sub.9 (n)                                                                      ##STR241##            dark blue             214  Br  COOC.sub.2 H.sub.5                                                                    CN    CN                                                                                          ##STR242##            blue                  215  Br  COOC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.9                                                                          ##STR243##            dark blue             216  Br  COOC.sub.2 H.sub.5                                                                    CN    CON(CH.sub.3).sub.2                                                                         ##STR244##            bluish violet         217  Br  CONH.sub.2                                                                            CN    COOC.sub.2 H.sub.5                                                                          ##STR245##            dark blue             218  Br  SO.sub.2 CH.sub.3                                                                     CN    COOC.sub.2 H.sub.5                                                                          ##STR246##            dark blue             219  Br  CON(CH.sub.3).sub.2                                                                   CN    COOC.sub.2 H.sub.5                                                                          ##STR247##            dark blue             220  Br  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR248##            dark blue             221  Br  CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR249##            blue                  222  Br  CN     CN    COOCH.sub.3                                                                                 ##STR250##            blue                  223  Br  CN     CN    COOCH.sub.3                                                                                 ##STR251##            navy blue             224  Cl  CN     CN                                                                                    ##STR252##                                                                                 ##STR253##            dark blue             225  F   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR254##            dark blue             226  F   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR255##            dark blue             227  F   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR256##            dark blue             228  F   COOC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                          ##STR257##            dark blue             229  OC.sub.2 H.sub.5                                                                   CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                          ##STR258##            dark blue             230  OC.sub.2 H.sub.5                                                                   CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                          ##STR259##            blue                  231  OC.sub.2 H.sub.5                                                                   CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                          ##STR260##            dark blue             232  OC.sub.2 H.sub.5                                                                   CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                          ##STR261##            blue                  233  OC.sub.2 H.sub.5                                                                   CN     CN    CN                                                                                          ##STR262##            dark blue             234  OC.sub.2 H.sub.5                                                                   CN     COCH.sub.3                                                                           COOC.sub.2 H.sub.5                                                                          ##STR263##            dark blue             235  OC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                          ##STR264##            blue                  236  OC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                          ##STR265##            dark blue             237  OC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                          ##STR266##            blue                  238  OC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                          ##STR267##            dark blue             239  OC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    COCH.sub.3                                                                           COOC.sub.2 H.sub.5                                                                          ##STR268##            dark blue             240  OC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    COCH.sub.3                                                                           COCH.sub. 3                                                                                 ##STR269##            bluish violet         241  OC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    COCH.sub.3                                                                           CN                                                                                          ##STR270##            dark blue             242  OC.sub.2 H.sub.5                                                                    ##STR271##                                                                           CN    COOC.sub.2 H.sub.5                                                                          ##STR272##            dark blue             243  OC.sub.2 H.sub.5                                                                    ##STR273##                                                                           CN    COOC.sub.2 H.sub.5                                                                          ##STR274##            blue                  244  OC.sub.2 H.sub.5                                                                   SO.sub.2 CH.sub.3                                                                     CN    COOC.sub.2 H.sub.5                                                                          ##STR275##            dark blue             245  OC.sub.2 H.sub.5                                                                   SO.sub.2 CH.sub.3                                                                     CN    COOC.sub.2 H.sub.5                                                                          ##STR276##            dark blue             246  OC.sub.2 H.sub.5                                                                   SO.sub.2 CH.sub.3                                                                     CN    COOC.sub.2 H.sub.5                                                                          ##STR277##            blue                  247  OC.sub.2 H.sub.5                                                                   CN     CN    CON(CH.sub.3).sub.2                                                                         ##STR278##            reddish blue          248  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR279##            reddish blue          249  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR280##            dark blue             250  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR281##            dark blue             251  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR282##            dark blue             252  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR283##            dark blue             253  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR284##            dark blue             254  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR285##            blue                  255  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR286##            blue                  256  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR287##            blue                  257  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.4 H.sub.9 (n)                                                                      ##STR288##            blue                  258  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.4 H.sub.9 (n)                                                                      ##STR289##            blue                  259  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.4 H.sub.9 (n)                                                                      ##STR290##            blue                  260  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.4 H.sub.9 (n)                                                                      ##STR291##            dark blue             261  OC.sub.2 H.sub.5                                                                   CN     CN                                                                                    ##STR292##                                                                                 ##STR293##            dark blue             262  OC.sub.2 H.sub.5                                                                   CN     CN                                                                                    ##STR294##                                                                                 ##STR295##            dark blue             263  OC.sub.2 H.sub.5                                                                   CN     CN                                                                                    ##STR296##                                                                                 ##STR297##            dark blue             264  OC.sub.2 H.sub.5                                                                   CN     CN    CONH.sub.2                                                                                  ##STR298##            dark blue             265  OC.sub.2 H.sub.5                                                                   CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                          ##STR299##            navy blue             266  OC.sub.2 H.sub.5                                                                   CN     COCH.sub.3                                                                           COOC.sub.2 H.sub.5                                                                          ##STR300##            dark blue             267  OC.sub.2 H.sub.5                                                                   CN     CN    CONHCH.sub.3                                                                                ##STR301##            dark blue             268  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR302##            navy blue             269  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR303##            violet                270  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR304##            violet                271  OC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR305##            violet                272  OC.sub.2 H.sub.5                                                                   CN     CN    CONHCH.sub.3                                                                                ##STR306##            dark blue             273  OC.sub.2 H.sub.5                                                                   CN     CN    CONHC.sub.2 H.sub.5                                                                         ##STR307##            dark blue             274  OC.sub.2 H.sub.5                                                                   CN     CN    SO.sub.2 CH.sub.3                                                                           ##STR308##            dark blue             275  OC.sub.2 H.sub.5                                                                   CN     CN    COCH.sub.3                                                                                  ##STR309##            dark blue             276  OC.sub.2 H.sub.5                                                                   CN     CN    COOCH.sub.3                                                                                 ##STR310##            dark blue             277  OCH.sub.3                                                                          CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR311##            bluish violet         278  OC.sub.6 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR312##            bluish violet         279  SC.sub.6 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR313##            bluish violet         280  SC.sub.6 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR314##            dark blue             281  OCH.sub.3                                                                          CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR315##            dark blue             282  OCH.sub.3                                                                          CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR316##            blue                  283  OCH.sub.3                                                                          CN     CN    COOC.sub.4 H.sub.9 (n)                                                                      ##STR317##            blue                  284  OC.sub.6 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR318##            dark blue             285  SC.sub.6 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR319##            dark blue             286  SC.sub.6 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR320##            dark blue             287  SC.sub.6 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR321##            dark blue             288  SC.sub.2 H.sub.5                                                                   CN     CN    COOC.sub.2 H.sub.5                                                                          ##STR322##            dark blue             289  SC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                          ##STR323##            dark blue             __________________________________________________________________________

EXAMPLE 290

a) 18.6 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene were suspended in 140 parts by volume of ethanol, and 2 parts of glacial acetic acid and 2 parts of piperidine were added. Thereafter, 50 parts by volume of ethyl cyanoacetate were added dropwise at room temperature and the mixture was stirred for 7 hours at 60° C. It was then introduced into 500 parts of an ice/water mixture, and the precipitate was filtered off under suction, washed with water and dried at 60° C. under reduced pressure to give 20 parts of 2-amino-4-chloro-3-cyano-5-(β-cyano-β-carboethoxyvinyl)-thiophene of the formula ##STR324## which was reacted without further purification.

b) 14 parts of this product were suspended in 100 parts by volume of 85% strength phosphoric acid, and 16 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were added slowly at 0°-5° C. After 2 hours at this temperature, the diazonium salt solution was run into a solution of 9.75 parts of N-cyanoethyl-N-ethyl-m-toluidine in a mixture of 125 parts of water, 500 parts of ice, 25 parts by volume of 32% strength hydrochloric acid and 1 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried under reduced pressure to give 20 parts of the dye described in Example 155, of the formula ##STR325## On polyesters, this dye gives dark blue dyeings having generally good fastness properties.

EXAMPLE 291

14.5 parts of 2-amino-3-cyano-4-ethoxy-5-(β-cyano-β-carboethoxyvinyl)-thiophene were suspended in 160 parts by volume of 85% strength phosphoric acid and diazotized with 16 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) at 0°-5° C. After 2 hours at this temperature, the diazonium salt solution was reacted with 9.75 parts of N-cyanoethyl-N-ethyl-m-toluidine similarly to Example 290 to give 20 parts of the dye of the formula ##STR326## which, on polyesters, gives blue dyeings possessing good lightfastness and fastness to dry heat pleating and setting.

EXAMPLE 292

14 parts of 2-amino-4-chloro-3-cyano-5-(β-cyano-β-methylaminocarbonyl)-vinyl)-thiophene were suspended in 120 parts by volume of 85% strength phosphoric acid and reacted with 16 parts of nitrosylsulfuric acid at 0°-5° C., and the mixture was stirred for 2 hours at this temperature. The diazonium salt solution was run slowly into a mixture of 7.5 parts of N,N-diethylaniline, 100 parts of water, 300 parts of ice, 25 parts by volume of 32% strength hydrochloric acid and 1 part of amidosulfonic acid. When coupling was complete, the suspension was filtered and the residue was washed neutral and dried to give 16 parts of the dye of the formula ##STR327## which, on polyesters, gives dark blue dyeings possessing generally good fastness properties.

The compounds characterized in the Table below were obtained similarly to Examples 290-292.

    __________________________________________________________________________      ##STR328##                                                                    Example                                                                        No.  X   Y     Y.sup.1                                                                           Y.sup.2                                                                              K                 *.sup.)                              __________________________________________________________________________     293  Br  CN    CN COOCH.sub.3                                                                           ##STR329##       dark blue                            294  Br  CN    CN COOCH.sub.3                                                                           ##STR330##       dark blue                            295  Br  CN    CN COOCH.sub.3                                                                           ##STR331##       blue                                 296  Br  CN    CN COOCH.sub.3                                                                           ##STR332##       blue                                 297  Cl  CN    CN COOC.sub. 2 H.sub.5                                                                   ##STR333##       dark blue                            298  Cl  CN    CN COOC.sub.2 H.sub.5                                                                    ##STR334##       dark blue                            299  Cl  CN    CN COOC.sub.2 H.sub.5                                                                    ##STR335##       dark blue                            300  Cl  CN    CN COOC.sub.2 H.sub.5                                                                    ##STR336##       dark blue                            301  Cl  CN    CN CONHCH.sub.3                                                                          ##STR337##       dark blue                            302  Cl  COOCH.sub.3                                                                          CN COOC.sub.2 H.sub.5                                                                    ##STR338##       dark blue                            303  Cl  SO.sub.2 CH.sub.3                                                                    CN COOC.sub.2 H.sub.5                                                                    ##STR339##       dark blue                            304  Cl  CN    CN COOC.sub.2 H.sub.5                                                                    ##STR340##       reddish blue                         305  F   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR341##       dark blue                            306  F   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR342##       dark blue                            307  F   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR343##       blue                                 308  Cl  CN    CN CN                                                                                    ##STR344##       blue                                 309  OC.sub.2 H.sub.5                                                                   CN    CN COOCH.sub.3                                                                           ##STR345##       dark blue                            310  OC.sub.2 H.sub.5                                                                   CN    CN COOCH.sub.3                                                                           ##STR346##       blue                                 311  OCH.sub.3                                                                          CN    CN COOC.sub.2 H.sub.5                                                                    ##STR347##       dark blue                            312  OC.sub.2 H.sub.5                                                                   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR348##       dark blue                            313  SC.sub.6 H.sub.5                                                                   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR349##       dark blue                            314  OC.sub.2 H.sub.5                                                                   CN    CN COOCH.sub.3                                                                           ##STR350##       dark blue                            315  SC.sub.6 H.sub.5                                                                   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR351##       dark blue                            __________________________________________________________________________      *.sup.) Dyeing on polyester                                              

The following dyes characterized by the substituents can also be prepared similarly to the methods described:

    __________________________________________________________________________     Example                                   Color on                             No.  T            X    Y  K               polyester                            __________________________________________________________________________     316  CHO          Cl   CN                                                                                 ##STR352##     blue                                 317  CHO          Cl   CN                                                                                 ##STR353##     greenish blue                        318  CHO          Cl   CN                                                                                 ##STR354##     blue                                 319  CHO          Cl   CN                                                                                 ##STR355##     blue                                 320  CHO          Cl   CN                                                                                 ##STR356##     blue                                 321  CHO          Cl   CN                                                                                 ##STR357##     blue                                 322  CHO          Br   CN                                                                                 ##STR358##     blue                                 323  CHO          Cl   CN                                                                                 ##STR359##     blue                                 324  CHO          Cl   CN                                                                                 ##STR360##     blue                                 325  CHO          Cl   CN                                                                                 ##STR361##     reddish blue                         326  CHO          Cl   CN                                                                                 ##STR362##     blue                                 327  CHO          Cl   CN                                                                                 ##STR363##     reddish blue                         328  CHO          Cl   CN                                                                                 ##STR364##     blue                                 329  CHO          Cl   CN                                                                                 ##STR365##     blue                                 330  CHO          Cl   CN                                                                                 ##STR366##     blue                                 331  CHO          Cl   CN                                                                                 ##STR367##     blue                                 332  CHO          Cl   CN                                                                                 ##STR368##     blue                                 333  CN           Cl   CN                                                                                 ##STR369##     blue                                 334  CN           Cl   CN                                                                                 ##STR370##     blue                                 335  NO.sub.2     Cl   CN                                                                                 ##STR371##     greenish blue                        336  NO.sub.2     Cl   CN                                                                                 ##STR372##     blue                                 337  NO.sub.2     Cl   CN                                                                                 ##STR373##     blue                                 338  CN           Cl   CN                                                                                 ##STR374##     blue                                 339  CN           Cl   CN                                                                                 ##STR375##     blue                                 340  CN           Cl   CN                                                                                 ##STR376##     blue                                 341  CHO          Cl   CN                                                                                 ##STR377##     blue                                 342  CHO          Cl   CN                                                                                 ##STR378##     blue                                 343  CHO          Cl   CN                                                                                 ##STR379##     reddish blue                         344  CHO          Cl   CN                                                                                 ##STR380##     blue                                 345  CHO          Cl   CN                                                                                 ##STR381##     blue                                 346  CHO          Br   CN                                                                                 ##STR382##     blue                                 347  CHO          Br   CN                                                                                 ##STR383##     blue                                 348  CHO          C.sub.6 H.sub.5 S                                                                   CN                                                                                 ##STR384##     reddish blue                         349  CHO          C.sub.6 H.sub.5 S                                                                   CN                                                                                 ##STR385##     greenish blue                        350  CHO          OC.sub.2 H.sub.5                                                                    CN                                                                                 ##STR386##     reddish blue                         351  CHO          C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                 ##STR387##     blue                                 352  CHO          C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                 ##STR388##     blue                                 353  CN           Cl   CN                                                                                 ##STR389##     reddish blue                         354  CN           Cl   CN                                                                                 ##STR390##     blue                                 355  H.sub.5 C.sub.2 O.sub.2 C(CN)CCH                                                            Cl   CN                                                                                 ##STR391##     blue                                 __________________________________________________________________________

EXAMPLE 356

2 parts of the dye described in Example 3, in 30 parts by volume of dimethylformamide and 50 parts by volume of glacial acetic acid, were stirred and 0.7 part of aniline was added. Stirring was continued for 12 hours at room temperature and 500 parts of water were added and the mixture was filtered under suction to give 2.2 parts of a powder of the formula ##STR392## which dyes polyester fabric in fast blue hues.

EXAMPLE 357

A suspension of 4 parts of the dye described in Example 3 in 50 parts by volume of dimethylformamide and 2 drops of concentrated sulfuric acid were added to 1.1 parts of phenylhydrazine in 40 parts by volume of ethanol. The mixture was stirred for 12 hours at 25° C., after which 500 parts of water were added and the dye of the formula ##STR393## was filtered off under suction and dried. 5 parts of a black powder which dyes polyester fabric in fast blue hues were obtained.

EXAMPLE 358

2.3 parts of the dye described in Example 23 were stirred in 50 parts by volume of formic acid, 0.5 part of hydroxylamine hydrochloride and 0.5 part of sodium formate for 12 hours at room temperature. 400 parts of water were added, after which the mixture was filtered under suction to give 2.4 parts of the dye of the formula ##STR394## which dyes polyester fabric in fast blue hues.

EXAMPLE 359

18.7 parts of 2-amino-3-cyano-4-chloro-5-formylthiophene in 120 parts by volume of glacial acetic acid and 40 parts by volume of propionic acid were stirred for 1 hour at room temperature, after which the mixture was cooled to 0°-5° C., 31 parts of 42% strength nitrosylsulfuric acid were added and stirring was continued for about one hour at this temperature.

The coupling component employed was obtained as follows: a thoroughly stirred mixture of 17 parts (based on dry substance) of water-moist 2-chloro-3-cyano-4-methyl-6-aminopyridine (obtained, for example, by the process described in German Patent 2,260,827), 20 parts by volume of isobutanol, 18 parts of 3-aminopropyl 4-hydroxybutyl ether and 8 parts of sodium carbonate was heated under a descending condenser for 5 hours at 145°-150° C. until a thin layer chromatogram showed that conversion was complete. The mixture was cooled to about 100° C., after which 35 parts of acetic acid were added dropwise and 15 parts of 96% strength sulfuric acid were introduced dropwise at 35°-40° C. with further slight cooling. Stirring was continued for 3 hours, after which about 92% of the hydroxy compound were found to be acetylated. The solution of the diazonium salt was run into a thoroughly stirred mixture of 100 parts of the resulting coupling component, 300 parts of ice and 100 parts of water, and stirring was continued for about 2 hours at 0°-5° C. until the diazonium salt solution had been consumed. Thereafter, the coupling mixture was filtered under suction and the residue was washed neutral and dried at 80° C. The greenish black powder contains about 90% of the compound of the formula ##STR395## [λ_(max) : 546 nm (9:1 dimethylformamide/acetic acid)] as well as about 10% of the non-acetylated hydroxy compound.

The dye mixture possesses very good tinctorial properties and, on polyester, gives very deep, brilliant, reddish violet dyes possessing very good lightfastness and fastness to plating.

EXAMPLE 360

When an equivalent amount of the coupling component described below was used under the preparation conditions of the above example, the reddish blue dye 9λ_(max) : 572 nm, 9:1 dimethylformamide/acetic acid) of the formula ##STR396## was obtained. The product still contained about 5% of the hydroxy compound.

The coupling component used was obtained as follows: 45 parts of 2-chloro-3-cyano-4-methyl-6-(3'-hydroxypropylamino)-pyridine (obtained as described in German Patent 2,260,827) were stirred in the presence of one part of p-toluenesulfonic acid in 37 parts of aniline for one hour at 125° C. A total of 10 parts of sodium carbonate were added at 135° C. in three portions at 10 minute intervals, and stirring was continued for about 4 hours at 145° C. until a thin layer chromatogram showed that conversion was complete. Excess aniline was distilled off under reduced pressure, and the hot melt was discharged on to 200 parts by volume of hot water. The aqueous solution was decanted, and the remaining melt was stirred several times with hot water containing acetic acid and was separated off cold. After drying, 14.2 parts of the melt, consisting of 2-phenylamino-3-cyano-4-methyl-6-(3'-hydroxypropylamino)pyridine, were dissolved in 50 parts by volume of glacial acetic acid, and 6 parts of 96% strength sulfuric acid were added dropwise. The mixture was stirred for 3 hours at 60° C., after which the solution was used directly in the coupling reaction described.

The dyes listed in Table I were also obtained in a similar manner, these dyes having a similar property spectrum. The λ_(max) values were determined in a 9:1 mixture of dimethylformamide and acetic acid.

                                      TABLE 1                                      __________________________________________________________________________      ##STR397##                                                                    Example                            λmax                                 No.  X       Y  R.sup.1 R.sup.2    [nm]                                        __________________________________________________________________________     361  Cl      CN H       C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOC.sub.2                                    H.sub.5    545.5                                       362  Cl      CN H       C.sub.3 H.sub.6 OC.sub.2 H.sub.7 OC.sub.2                                                 547ub.5                                     363  Cl      CN H       C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4                                                 546.8.9                                     364  Cl      CN C.sub.2 H.sub.4 OCH.sub.3                                                               ##STR398##                                                                               565                                         365  Cl      CN                                                                                 ##STR399##                                                                             ##STR400##                                                                               567                                         366  Cl      CN                                                                                 ##STR401##                                                                             ##STR402##                                                                               573                                         367  OC.sub.2 H.sub.5                                                                       CN H       C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              538                                         368  OC.sub.2 H.sub.5                                                                       CN H       C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                                 540ub.5                                     369  OC.sub.2 H.sub.5                                                                       CN C.sub.3 H.sub.6 OCOCH.sub.3                                                             ##STR403##                                                                               560.5                                       370  OC.sub.2 H.sub.5                                                                       CN C.sub.3 H.sub.6 OH                                                                      ##STR404##                                                                               569                                         371                                                                                  ##STR405##                                                                            CN H       C.sub.3 H.sub.6 OC.sub.4 H.sub.6 OCOCH.sub.3                                              540                                         372                                                                                  ##STR406##                                                                            CN H       C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              540                                         __________________________________________________________________________

EXAMPLE 373

14.6 parts of 2-amino-3-cyano-4-ethoxy-5-(2'-cyano-2'-carbethoxyvinyl)-thiophene were diazotized similarly to the procedure described in Example 359 but using half the amount of reagents and assistants, and the product was coupled to 2-(4'-acetoxybutoxy)-3'-propylamino-3-cyano-4-methyl-6-aminopyridine. This gives a bluish black powder of the formula ##STR407## which still contains about 10% of the hydroxy compound and dyes polyester materials in medium blue hues which have very good lightfastness, fastness to washing and fastness to plating.

The diazo component was obtained as follows: 60 parts of 2-amino-3-cyano-4-ethoxythiophene-5-carbaldehyde in 200 parts by volume of dimethylformamide and 57 parts of ethyl cyanoacetate were stirred at room temperature. 10 parts by volume of a saturated aqueous sodium acetate solution were added dropwise, and stirring was continued for 2 hours at 40° C. Precipitation was completed by adding 1,000 mL of ice-cold methanol, and the product was filtered off, washed first with ice-cold methanol and then with water, and dried at 60° C. Yield: 60 parts (67.4%).

EXAMPLE 374

The procedure described in Example 359 was used, but with half the amount of reagents and assitants, and 14.1 parts of 2-amino-3-cyano-4-chloro-5-(2'-cyano-2'-carbethoxyvinyl)-thiophene were diazotized and the product coupled to 2-(4'-acetoxybutoxy)-3'-propylamino-3-cyano-4-methyl-6-(3'-acetoxypropylamino)-pyridine.

This gives a black powder which consists of 90% of the compound of the formula ##STR408## (λ_(max) =585.5 nm; acetone) and dyes polyester in medium blue hues which have very good lightfastness, fastness to washing and fastness to plating.

The diazo component was obtained by a method similar to that described in Example 373, and the coupling component was obtained as follows:

45 parts of 2-chloro-3-cyano-4-methyl-6-(3'-hydroxypropylamino)-pyridine (obtained as described in German Patent 2,260,827) were stirred for 5 hours at 145° C. in the presence of 14 parts of sodium carbonate in 33 parts of 3-aminopropyl 4-hydroxybutyl ether, and the mixture was cooled to 100° C. and discharged on to 120 parts by volume of glacial acetic acid. 41 g of 96% strength sulfuric acid were then added dropwise at 30° C. The mixture was stirred for 3 hours at 40° C., after which a quarter of the solution was converted to the dye, as described above.

The dyes in Table 2, which have similar properties, were obtained in a similar manner. The λ_(max) values were determined in acetone, except for those marked with *, which were measured in a 9:1 dimethylformamide/acetic acid mixture.

                                      TABLE 2                                      __________________________________________________________________________      ##STR409##                                                                    Example                                 λmax                            No.  T     X   Y  R.sup.1    R.sup.2    [nm]                                   __________________________________________________________________________     375  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN H          C.sub.3 H.sub.6 OCH.sub.3                                                                 583                                    376  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN H                                                                                          ##STR410##                                                                               580.5                                  377  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN H          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                      H.sub.5    594*                                   378  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              597*                                   379  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN C.sub.2 H.sub.4 OH                                                                        C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                      H.sub.5    602.3*                                 380  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                C.sub.3 H.sub.4 OCOCH.sub.3                                                               591.5                                  381  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN C.sub.2 H.sub.4 OCOCH.sub.3                                                               C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                      H.sub.5    591.5                                  382  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              594                                    383  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              594                                    384  CN    OC.sub.2 H.sub.5                                                                   CN H          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              583                                    385  CN    OC.sub.2 H.sub.5                                                                   CN C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OC.sub.4 H.sub.6 OCOCH.sub.3                                              595                                    386  CN    OC.sub.2 H.sub.5                                                                   CN C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              595                                    387  CN    Cl  CN C.sub.3 H.sub.6 OCOCH.sub.3                                                                ##STR411##                                                                               613.5*                                 388  CN    Cl  CN C.sub.3 H.sub.4 OH                                                                        C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                      H.sub.5    605.3*                                 389  CN    Cl  CN H          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                      H.sub.5    578                                    390  COOCH.sub.3                                                                          Cl  CN H          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              577                                    391  COOC.sub.2 H.sub.5                                                                   Cl  CN H          C.sub.3 H.sub.6 OCH.sub.3                                                                 578                                    392  COOC.sub.2 H.sub.5                                                                   Cl  CN H                                                                                          ##STR412##                                                                               575.5                                  393  COOC.sub.2 H.sub.5                                                                   Cl  CN H                                                                                          ##STR413##                                                                               588                                    394  CN    Cl  CN C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              586                                    395  COOC.sub.2 H.sub.5                                                                   Cl  CN C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4                                      H.sub.9    588                                    396  COOC.sub.2 H.sub.5                                                                   Cl  CN C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              585.5                                  397  COOC.sub.2 H.sub.5                                                                   Cl  CN C.sub.2 H.sub.4 OCOCH.sub.3                                                               C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                      H.sub.5    586                                    398  COOC.sub.2 H.sub.5                                                                   Cl  CN C.sub.3 H.sub.8 OC.sub.4 H.sub.8 OCOCH.sub.3                                               ##STR414##                                                                               612*                                   399  CN    Cl  CN C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              C.sub.3 H.sub.8 OC.sub.4 H.sub.8 OCOCH.sub.3                                              586                                    __________________________________________________________________________

EXAMPLE 400

7.3 parts of 2-amino-3-cyano-5-formyl-4-phenylsulfonylthiophene in 30 parts by volume of 85% strength sulfuric acid were stirred at no higher than 30° C. 8.3 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were added dropwise at 0°-5° C., after which stirring was continued for 4 hours at this temperature.

This diazonium salt solution was diluted with 20 ml of concentrated sulfuric acid and then run slowly, at 0° C., into a solution of 6.6 parts of 3-[N,N-di-n-butylamino]-acetanilide in a mixture of 25 parts by volume of dimethylformamide, 125 parts of water, 300 parts of ice and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried, and 12 parts of the dye of the formula ##STR415## were obtained. This dye dyes polyester fibers in fast blue hues.

EXAMPLE 401

7.3 parts of 2-amino-3-cyano-5-formyl-4-phenylsulfonylthiophene were diazotized by a method similar to that described in the Example above.

The diazonium salt solution was added dropwise, at 0° C., to a solution of 5.2 parts of 3-(N,N-diethylamino)-acetanilide in a mixture of 125 parts of water, 350 parts of ice, 10 parts by volume of 32% strength hydrochloric acid and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried, and 10.5 parts of a powder of the formula ##STR416## were obtained. This dye dyes polyester fabric in fast blue hues.

The dyes shown in the Table below were obtained in a similar manner.

    __________________________________________________________________________      ##STR417##                                                                    Example No.                                                                           T    X           Y      K                     Dyeing on                 __________________________________________________________________________                                                          polyester                 402    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR418##           greenish blue             403    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR419##           bluish violet             404    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR420##           blue                      405    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR421##           blue                      406    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR422##           blue                      407    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR423##           reddish blue              408    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR424##           bluish violet             409    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR425##           greenish blue             410    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR426##           blue                      411    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR427##           blue                      412    CHO  C.sub. 6 H.sub.5 SO.sub.2                                                                  CO.sub.2 C.sub.2 H.sub.5                                                               ##STR428##           blue                      413    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR429##           blue                      414    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR430##           blue                      415    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR431##           blue                      416    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR432##           blue                      417    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR433##           blue                      418    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR434##           blue                      419    CHO                                                                                  ##STR435## CO.sub.2 C.sub.2 H.sub.5                                                               ##STR436##           reddish blue              420    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR437##           blue                      421    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CONH.sub.2                                                                             ##STR438##           blue                      422    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   NO.sub.2                                                                               ##STR439##           blue                      423    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CON(CH.sub.3).sub.2                                                                    ##STR440##           blue                      424    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   SO.sub.2 CH.sub.3                                                                      ##STR441##           blue                      425    CHO  CH.sub.3 SO.sub.2                                                                          CO.sub.2 C.sub.2 H.sub.5                                                               ##STR442##           blue                      426    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR443##           blue                      427    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR444##           blue                      428    CHO  CH.sub.3 SO.sub.2                                                                          CN                                                                                     ##STR445##           blue                      429    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR446##           violet                    430    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR447##           blue                      431    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR448##           blue                      432    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR449##           yellowish brown           433    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR450##           red                       434    CHO  C.sub.6 H.sub. 5 SO.sub.2                                                                  CN                                                                                     ##STR451##           red                       435    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR452##           blue                      436    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR453##           blue                      437    CHO  p-ClC.sub.6 H.sub.4 SO.sub.2                                                               CN                                                                                     ##STR454##           blue                      438    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR455##           blue                      439    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR456##           violet                    440    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR457##           red                       441    CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR458##           red                       442    CN   C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR459##           blue                      443    CN   C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR460##           blue                      444    CN   C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR461##           greenish blue             445    CN   CH.sub.3 SO.sub.2                                                                          CN                                                                                     ##STR462##           reddish blue              446    CN   C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR463##           blue                      447    NO.sub.2                                                                            C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR464##           reddish blue              448    NO.sub.2                                                                            C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR465##           blue                      449    NO.sub.2                                                                            C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR466##           blue                      450    NO.sub.2                                                                            C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR467##           greenish blue             451                                                                                    ##STR468##                                                                         C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR469##           blue                      452    Cl   C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR470##           reddish blue              453    Br   CH.sub.3 SO.sub.2                                                                          CN                                                                                     ##STR471##           reddish                   __________________________________________________________________________                                                          blue                 

EXAMPLE 454

1.2 parts of sodium phenylsulfinate were added to 2.3 parts of 4-chloro-3-cyano-5-formyl-2-(4'-N,N-dibutylamino-2'-acetylaminophenylazo)-thiophene in 50 parts by volume of dimethylformamide, and the mixture was stirred at room temperature. When the reaction was complete (thin layer chromatogram), the reaction mixture was poured on to 300 parts of water, and the dye formed was isolated. 2.4 parts of the dye of the formula ##STR472## were obtained. This dye dyes polyester fibers in fast blue hues.

The dyes shown in the Table below were obtained by a method similar to Example 454.

    __________________________________________________________________________      ##STR473##                                                                    Example                             Dyeing on                                  No.  T   X    Y    K                polyester                                  __________________________________________________________________________     455  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR474##      blue                                       456  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR475##      bluish violet                              457  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR476##      blue                                       458  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR477##      blue                                       459  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR478##      blue                                       460  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR479##      blue                                       461  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR480##      reddish blue                               462  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR481##      reddish blue                               463  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CO.sub.2 C.sub.5 H.sub.5                                                             ##STR482##      blue                                       __________________________________________________________________________

EXAMPLE 464

2.6 parts of the dye described in Example 413 were dissolved in 80 parts by volume of dioxane, 1.1 parts of ethyl cyanoacetate, 0.4 part of glacial acetic acid and 0.4 part of piperidine were added, and the mixture was stirred for 16 hours at room temperature. 50 parts of water and 50 parts of ice were then added, stirring was continued for 15 minutes, and the product was filtered off under suction, washed neutral and dried at 50° C. under reduced pressure to give 2.8 parts of the dye of the formula ##STR483## which dyes polyester fibers in fast blue hues.

EXAMPLE 465

2.3 parts of the dye described in Example 403 were dissolved in 70 parts by volume of dioxane, 1.4 parts of butyl cyanoacetate, 0.4 part of glacial acetic acid and 0.4 part of piperidine were added and the mixture was stirred for 16 hours at room temperature. 50 parts of water and 50 parts of ice were then added, stirring was continued for 1 hour and the product was filtered off under suction, washed neutral and dried to give 2.5 parts of the dye of the formula ##STR484## which dyes polyester fabric in fast blue hues.

The dyes shown in the Table below were obtained similarly to the above Examples.

    __________________________________________________________________________      ##STR485##                                                                    Example                                                  Dyeing on             No.   X       Y     Y.sup.2                                                                             Y.sup.3    K                    polyester             __________________________________________________________________________     466   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   CN                                                                                         ##STR486##          blue                  467   C.sub.6 H.sub.5 SO.sub.2                                                               CN    COCH.sub.3                                                                          COOC.sub.2 H.sub.5                                                                         ##STR487##          blue                  468   C.sub.6 H.sub.5 SO.sub.2                                                               COOC.sub.2 H.sub.5                                                                   CN   COOC.sub.2 H.sub.5                                                                         ##STR488##          blue                  469   C.sub.6 H.sub.5 SO.sub.2                                                               COOC.sub.2 H.sub.5                                                                   CN   COOC.sub.2 H.sub.5                                                                         ##STR489##          blue                  470   C.sub.6 H.sub.5 SO.sub.2                                                               COOC.sub.2 H.sub.5                                                                   CN   COOC.sub.2 H.sub.5                                                                         ##STR490##          blue                  471   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR491##          reddish blue          472   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR492##          blue                  473   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR493##          blue                  474   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR494##          blue                  475   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR495##          blue                  476   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR496##          violet                477   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR497##          violet                478   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR498##          violet                479   C.sub.6 H.sub. 5 SO.sub.2                                                              CN    CN   CONHCH.sub.3                                                                               ##STR499##          blue                  480   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   CONHC.sub.2 H.sub.5                                                                        ##STR500##          blue                  481   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   SO.sub.2 CH.sub.3                                                                          ##STR501##          blue                  482   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   COCH.sub.3                                                                                 ##STR502##          blue                  483   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   COOCH.sub.3                                                                                ##STR503##          blue                  484   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   COOC.sub.4 H.sub.9 (n)                                                                     ##STR504##          greenish blue         485   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   COOC.sub.4 H9(n)                                                                           ##STR505##          greenish blue         486   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   COOC.sub.4 H.sub.9 (n)                                                                     ##STR506##          blue                  487   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   COOC.sub.4 H.sub.9 (n)                                                                     ##STR507##          blue                  488   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN                                                                                   ##STR508##                                                                                ##STR509##          blue                  489   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN                                                                                   ##STR510##                                                                                ##STR511##          blue                  490   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN                                                                                   ##STR512##                                                                                ##STR513##          blue                  491   C.sub.6 H.sub.5 SO.sub.2                                                               CN    CN   CONH.sub.2                                                                                 ##STR514##          blue                  492   CH.sub.3 SO.sub.2                                                                      CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR515##          blue                  493   CH.sub.3 SO.sub.2                                                                      CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR516##          blue                  494   CH.sub.3 SO.sub.2                                                                      CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR517##          blue                  495   p-ClC.sub.6 H.sub.4 SO.sub.2                                                           CN    CN                                                                                   ##STR518##                                                                                ##STR519##          blue                  __________________________________________________________________________

EXAMPLE 496

a) 14.6 parts of 2-amino-3-cyano-5-formyl-4-phenylsulfonylthiophene were suspended in 50 parts by volume of ethanol, and 1 part of glacial acetic acid and 1 part of piperidine were added. 13 parts by volume of ethyl cyanoacetate were then added dropwise at room temperature, and the mixture was stirred for 5 hours at 60° C. The reaction mixture was poured on to 800 parts of water, and the precipitate was filtered off under suction, washed with water and dried at 50° C. under reduced pressure to give 16 parts of 2-amino-3-cyano-4-phenylsulfonyl-5-(β-cyano-β-carboethoxyvinyl)-thiophene of the formula ##STR520## which was reacted without further purification.

b) 3.9 parts of 2-amino-3-cyano-4-phenylsulfonyl-5-(β-cyano-β-carboethoxyvinyl)-thiophene in 35 parts by volume of a 3:1 glacial acetic acid/propionic acid mixture were stirred, and 3.5 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were slowly added at 0°-5° C. After 2 hours at this temperature, the diazonium salt solution was run into a solution of 2 parts of N-cyanoethyl-N-ethyl-m-toluidine in a mixture of 25 parts of water, 100 parts of ice, 5 parts by volume of 32% strength hydrochloric acid and 0.2 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried under reduced pressure. 4.5 parts of the dye of the formula ##STR521## were obtained. On polyester fibers, this dye gives blue dyeings having in general very good fastness properties.

EXAMPLE 497

3.4 parts of 2-amino-3-cyano-4-phenylsulfonyl-5-(β,β-dicyanovinyl)-thiophene were suspended in 25 parts by volume of 85% strength phosphoric acid and slowly reacted with 3.5 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) at 0°-5° C., and the mixture was stirred for 2 hours at this temperature. This diazonium salt solution was run slowly into a mixture of 1.5 parts of N,N-diethylaniline, 20 parts of water, 60 parts of ice, 5 parts by volume of 32% strength hydrochloric acid and 0.2 part of amidosulfonic acid. When coupling was complete, the suspension was filtered and the dye was washed neutral and dried. 4.2 parts of the dye of the formula ##STR522## were obtained. On polyesters, this dye gives blue dyeings having generally good fastness properties.

The compounds shown in the Table below were obtained in a similar manner.

    __________________________________________________________________________      ##STR523##                                                                    Example                                    Dyeing on                           No.  X    Y     Y.sup.2                                                                           Y.sup.3                                                                              K                 polyester                           __________________________________________________________________________     498  CH.sub.3 SO.sub.2                                                                   CN    CN COOCH.sub.3                                                                           ##STR524##       blue                                499  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN COOCH.sub.3                                                                           ##STR525##       blue                                500  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN COOCH.sub.3                                                                           ##STR526##       greenish blue                       501  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN COOCH.sub.3                                                                           ##STR527##       greenish blue                       502  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN COOC.sub.2 H.sub.5                                                                    ##STR528##       blue                                503  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN COOC.sub.2 H.sub.5                                                                    ##STR529##       blue                                504  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN COOC.sub.2 H.sub.5                                                                    ##STR530##       blue                                505  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN COOC.sub.2 H.sub.5                                                                    ##STR531##       greenish blue                       506  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN CONHCH.sub.3                                                                          ##STR532##       blue                                507  C.sub.6 H.sub.5 SO.sub.2                                                            COOCH.sub.3                                                                          CN COOC.sub.2 H.sub.5                                                                    ##STR533##       blue                                __________________________________________________________________________

Examples of suitable dischargeable dyes are the compounds of Examples 21, 22, 113 and 114 and those of Examples 341-355. 

We claim:
 1. A compound of the formula: ##STR534## wherein X is fluorine, chlorine or bromine;Y is cyano; T is hydrogen; C₁ -C₄ -alkyl; Cl; Br; NO; NO₂ ; SO₃ H; CHO; CN; CH₃ CO; C₂ H₅ CO; C₆ H₅ CO; CH₃ SO₂ ; C₂ H₅ SO₂ ; C₆ H₅ SO₂ ; or --CH═B; B is C(CN) (Z) where Z is cyano; nitro; alkanoyl; aroyl; alkylsulfonyl; arylsulfonyl; carboxyl; a carboxylic ester group; unsubstituted carbamyl; substituted carbamyl; or a radical of a compound of one of the formulae: ##STR535## and K is a radical derived from a coupling component of the formula: ##STR536## wherein: B¹ is hydrogen or B² ;B² is C₁ -C₆ -alkyl, C₁ -C₆ -alkyl substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, phenyl, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy, phenylethoxycarbonyl, phenyl, or cyclohexyl; and R⁶ is cyano; carbamyl; nitro; acetyl; alkoxycarbonyl; methylaminocarbonyl; dimethylaminocarbonyl; ethylaminocarbonyl; diethylaminocarbonyl; methoxyethoxycarbonyl; ethoxyethoxycarbonyl; n-propoxyethoxycarbonyl; isopropoxyethoxycarbonyl; n-butoxyethoxycarbonyl; isobutoxyethoxycarbonyl; or sec.-butoxyethoxycarbonyl.
 2. The compound of claim 1, wherein X is fluorine.
 3. The compound of claim 1, wherein X is chlorine.
 4. The compound of claim 1, wherein X is bromine.
 5. The compound of claim 1, wherein T is hydrogen or C₁₋₄ alkyl.
 6. The compound of claim 1, wherein T is Cl or Br.
 7. The compound of claim 1, wherein T is NO or NO₂.
 8. The compound of claim 1, wherein T is SO₃ H, CH₃ SO₂, C₂ H₅ SO₂ or C₆ H₅ SO₂.
 9. The compound of claim 1, wherein T is CHO, CH₃ CO, C₂ H₅ CO or C₆ H₅ CO.
 10. The compound of claim 1, wherein T is CN.
 11. The compound of claim 1, wherein T is --CH═B, wherein B is as defined above.
 12. The compound of claim 1, wherein R⁶ is cyano.
 13. The compound of claim 1, wherein R⁶ is carbamyl.
 14. The compound of claim 1, wherein R⁶ is nitro.
 15. The compound of claim 1, wherein R⁶ is acetyl.
 16. The compound of claim 1, wherein R⁶ is alkoxycarbonyl.
 17. The compound of claim 1, wherein R⁶ is selected from the group consisting of aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec.-butoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, n-propoxyethoxycarbonyl, isopropoxyethoxycarbonyl, n-butoxyethoxycarbonyl, isobutoxyethoxycarbonyl and sec.-butoxyethoxycarbonyl. 